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Binary mixtures of 1,3-dialkylimidazolium based ionic liquids (ILs) and water were selected as solvent systems to investigate the solute-solvent and solvent-solvent interactions on the preferential solvation of solvatochromic indicators at 25℃. Empirical solvatochromic parameters, dipolarity/polarizability (π*), hydrogen-bond donor acidity (α), hydrogen-bond acceptor basicity (β), and Reichardt''s polarity parameters (ETN) were measured from the ultraviolet-visible spectral shifts of 4-nitroaniline, 4-nitroanisole, and Reichardt''s dye. The solvent properties of the IL-water mixtures were found to be influenced by IL type and IL mole fraction (xIL). All these studied systems showed the non-ideal behavior. The maximum deviation to ideality for the solvatochromic parameters can be obtained in the xIL range from 0.1 to 0.3. For most of the binary mixtures, the π* values showed the synergistic effects instead of the ETN, α and β values. The observed synergy extent was dependent on the studied systems, such as the dye indicator and IL type. A preferential solvation model was utilized to gather information on the molecular interactions in the mixtures. The dye indicator was preferentially solvated on the following trend: IL >IL-water complex >water.  相似文献
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Molecular interactions of the ternary mixtures of 1-butyl-3-methylimidazolium chloride ([C4C1im]Cl)-water-2,6-dimethoxyphenol (2,6-DMP, a phenolic monomer lignin model compound) were investigated in comparison with the [C4C1im]Cl-water binary systems through attenuated total reflection infrared spectroscopy. Results indicated that the microstructures of water and [C4C1im]Cl changed with varying mole fraction of [C4C1im]Cl (xIL) from 0.01 to 1.0. This change was mainly attributed to the interactions of [C4C1im]Cl-water and the self-aggregation of [C4C1im]Cl through hydrogen bonding. The band shifts of C-H on imidazolium ring and the functional groups in 2,6-DMP indicated that the occurrence of intermolecular interactions by different mechanisms (i.e., hydrogen bonding or π-π stacking) resulted in 2,6-DMP dissolution. In the case of xIL=0.12, the slightly hydrogen-bonded water was fully destroyed and [C4C1im]Cl existed in the form of hydrated ion pairs. Interestingly, the maximum 2,6-DMP solubility (238.5 g/100 g) was achieved in this case. The interactions and microstructures of [C4C1im]Cl-water mixtures influenced the dissolution behavior of 2,6-DMP.  相似文献
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